荧光分析问题

Click to edit Master title style,Click to edit Master text styles,Click to edit Master text styles,Second level,second level,second level,second level,second level,Third level,Third level,Third level,Third level,Third level,Third level,*,华新水泥股份有限公司技术中心,*,引起荧光分析结果准确性问题探讨,中心实验研究室,张攸沙,2010,年,06,月,21,日,引起荧光分析结果准确性的因素,标准曲线的质量,标准样品浓度值准确度,标准样品浓度范围,标准样品个数和间距,漂移校正分析,样片制备,分析天平,试样与熔剂比列,熔剂烧失量,融样机的条件,荧光分析标准曲线质量问题,国家标准规定,线性,(JC/T1085-2008,水泥用,X,射线荧光分析仪,),制作氧化钙的工作曲线时,各标准样品中氧化钙含量计算值与标准值之间误差的最大值应小于,0.17%;,制作二氧化硅的工作曲线时,各标准样品中二氧化硅含量计算值与标准值之间误差的最大值应小于,0.25%;,制作三氧化硫的工作曲线时,各标准样品中三氧化硫含量计算值与标准值之间误差的最大值应小于,0.10%;,(,不包含剔除值,),荧光分析标准曲线质量问题,校准方程的确认,(GB/T176-2008,水泥化学分析方法,),用未参加校准曲线建立的另一标准样品进行测定。对于所有的被测元素，浓度的测定值与标准样品、标准物质的证书值之差应小于重复性限（见下表）的,0.71,倍，确认校正曲线有效，否则无效，应重新制作。,化学成分,SiO2,Al2O3,Fe2O3,TiO2,CaO,MgO,SO3,K2O,Na2O,重复性限,%,0.20,0.14,0.20,0.14,0.15,0.11,0.05,0.25,0.18,0.15,0.11,0.15,0.10,0.05,再现性限,%,0.25,0.30,0.20,0.10,0.40,0.25,0.20,0.15,0.10,荧光分析标准曲线质量问题,石灰石标准曲线,(18,个标准样品,),建于,2009.11.24,CaO,(,删除,9,个点,“,”,包括紫色为,2010.6.8,补点,),C(Calc,),C(Chem,),diff,C(Calc,),C(Chem,),diff,45.83,48.08,-2.25,55.44,55.24,0.20,41.84,44.84,-3.00,44.09,44.98,-0.89,50.14,51.72,-1.58,53.91,53.98,-0.07,48.11,49.25,-1.14,50.22,50.29,-0.07,54.95,54.72,0.23,49.70,50.07,-0.37,28.97,28.72,0.24,51.65,52.20,-0.55,35.00,35.40,-0.40,46.33,46.02,0.31,43.42,42.69,0.73,42.24,40.72,1.52,51.44,51.53,0.09,48.29,48.90,-0.61,荧光分析标准曲线质量问题,石灰石标准曲线,(18,个标准样品,),MgO,C(Calc,),C(Chem,),diff,C(Calc,),C(Chem,),diff,0.91,1.00,-0.09,0.79,0.81,-0.02,1.24,1.18,0.06,0.28,0.24,0.04,0.90,1.03,-0.13,0.50,0.53,-0.03,1.06,1.18,-0.12,0.27,0.26,0.01,0.92,0.94,-0.02,0.64,0.64,0.00,0.15,0.11,0.04,0.85,0.89,-0.04,18.82,18.44,0.38,1.69,1.65,0.04,12.71,13.00,-0.29,5.38,5.42,-0.04,8.80,8.91,-0.11,10.83,10.58,0.25,荧光分析标准曲线质量问题,石灰石,CaO,标准曲线问题,:,各标准样品中氧化钙含量计算值与标准值之间误差的大多数点的最大值大于国家标准,(,应小于,0.17%);,各点浓度之间间隔太大,;,补点方法有问题。后加四点全部删除,石灰石,MgO,标准曲线问题,:,浓度范围太广，,MgO,含量,0.11,18.44%,；,各点浓度之间间隔太大，而且分布非常不均匀。,荧光分析标准曲线质量问题,生料标准曲线,(9,个标准样品,),建于,2009.11.24,SiO2,CaO,C(Calc,),C(Chem,),diff,C(Calc,),C(Chem,),diff,12.34,12.56,-0.22,43.57,43.17,0.40,15.53,15.67,-0.13,42.46,42.63,-0.17,13.78,13.63,0.15,44.35,43.77,0.58,10.30,10.35,-0.05,46.45,46.64,-0.19,14.35,14.39,-0.04,43.49,43.15,0.34,12.88,12.72,0.16,44.76,44.82,-0.06,10.62,10.61,0.01,46.09,45.77,0.32,11.81,11.79,0.02,44.83,45.14,-0.31,12.08,12.21,-0.13,43.50,43.84,-0.34,荧光分析标准曲线质量问题,建议：,按照国家标准严格执行,不合格点要查找原因,(,浓度值或制样、元素间干扰？）；,用不同含量（高、中、低）标准样品验证工作曲线的有效性,;,每种物料的标准曲线增加点,补点的方法,?,漂移校正的问题,2009.11.24,制作生料曲线，用,GB 03203a,生料标准样分析,化学成分,SiO2,Al2O3,Fe2O3,CaO,MgO,SO3,K2O,Na2O,标准值,11.71,2.95,1.84,44.64,0.97,0.06,0.62,0.09,2009.11.24,11.63,2.85,1.86,44.60,0.98,0.16,0.74,0.03,2010.09.08,未做漂移校正,11.23,2.73,1.85,44.31,0.94,0.15,0.73,0.03,2010.09.08,做漂移校正后,11.45,2.79,1.86,44.55,0.95,0.15,0.74,0.03,漂移校正的问题,H1OO01194,生料,化学成分,SiO2,Al2O3,Fe2O3,CaO,MgO,SO3,K2O,Na2O,未做漂移校正,12.33,2.69,1.89,41.53,1.79,做漂移校正后,11.57,2.75,1.91,41.84,1.79,0.16,0.74,0.03,漂移校正的问题,建议：,定期做漂移校正，每周一次？每旬一次？半个月一次,?,负责人：,?,记录,样片制备的问题,分析天平,误差,0.5mg,试样与熔剂比例,化学成分,熔片质量,g,SiO2,Al2O3,Fe2O3,CaO,MgO,SO3,K2O,Na2O,2,：,8,试样：熔剂,9.2440,（新）,11.81,3.59,1.87,45.36,1.02,0.23,0.74,0.02,2,：,8.7354,试样：熔剂,9.7960,（新）,11.26,3.01,1.84,44.18,0.94,0.30,0.72,0.02,2,：,8.7354,试样：熔剂,9.9744,（旧）,11.29,3.52,1.87,44.10,0.98,0.13,0.71,0.02,样片制备的问题,注意,：,熔片生料时，熔剂质量,=8+,生料烧失量*,2%,；,称完试样再称熔剂时，要注意分析天平归零；,熔剂烧失量：,要求：熔剂烧失量,0.5%,。,熔剂有结块现象，烧失量是否有变化？使用前是否处理,？,（在,650,高温炉灼烧,2,小时，放在 干燥器备用）,样片制备的问题,熔片机的条件,：通过漂移校正后,分析结果,生料结果：,化学成分,熔片质量,g,SiO2,Al2O3,Fe2O3,CaO,MgO,K2O,Na2O,标准值,11.71,2.95,1.84,44.64,0.97,0.62,0.09,新碟子,-1,9.7960,11.41,3.08,1.84,44.38,0.97,0.72,0.02,旧碟子,-1,9.9744,11.51,3.62,1.88,44.44,0.98,0.72,0.03,旧碟子,-2,10.0002,11.49,3.50,1.87,44.31,0.98,0.71,0.02,新碟子,-2,10.0120,11.11,3.52,1.82,43.24,0.95,0.71,0.02,样片制备的问题,熔片机的条件,：通过漂移校正后,分析结果,GSB08-1345-2006,石灰石,化学成分,熔片质量,g,SiO2,Al2O3,Fe2O3,CaO,MgO,K2O,Na2O,标准值,4.55,1.07,0.48,50.87,1.03,0.45,0.06,旧碟子,-1,9.4956,4.42,1.44,0.48,49.16,1.12,0.50,0.03,新碟子,-1,9.4892,4.63,1.32,0.51,49.46,1.12,0.50,0.03,新碟子,-2,9.3936,4.30,1.36,0.47,48.54,1.10,0.49,0.01,样片制备的问题,建议：,加强对比工作,。将以前熔片用荧光分析仪测定，测定结果与以前测定结果相同，说明荧光分析仪正常。另外用同一试样重新熔片，再用荧光分析仪测定，如果测定结果与前熔片结果相同，说明熔片机正常。,注意分析结果总和。,当分析结果异常时，先用标准样品在荧光分析测定，如果测定正常，就重新熔片。,